EP0781162B1 - Procede et systeme d'extraction d'un solute d'un fluide a l'aide d'un gaz dense et d'une membrane poreuse - Google Patents

Procede et systeme d'extraction d'un solute d'un fluide a l'aide d'un gaz dense et d'une membrane poreuse Download PDF

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Publication number
EP0781162B1
EP0781162B1 EP95908530A EP95908530A EP0781162B1 EP 0781162 B1 EP0781162 B1 EP 0781162B1 EP 95908530 A EP95908530 A EP 95908530A EP 95908530 A EP95908530 A EP 95908530A EP 0781162 B1 EP0781162 B1 EP 0781162B1
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European Patent Office
Prior art keywords
fluid
membrane
dense gas
solute
module
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EP95908530A
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German (de)
English (en)
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EP0781162A1 (fr
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James R. Robinson
Marc J. Sims
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Porocrit LLC
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MARC SIMS SFE
Tastemaker Inc
Separation Equipment Technologies Inc
Givaudan Roure Flavors Corp
Porocrit LLC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/24—Dialysis ; Membrane extraction
    • B01D61/246—Membrane extraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/002—Forward osmosis or direct osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • B01D71/16—Cellulose acetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/261—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/262—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/48—Polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/50—Polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/10—Temperature control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/14—Pressure control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • B01D2325/02832—1-10 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • B01D2325/02833—Pore size more than 10 and up to 100 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • B01D2325/02834—Pore size more than 0.1 and up to 1 µm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness

Definitions

  • This invention relates to fluid extraction and, more particularly, to extraction of solutes employing a hollow fiber membrane module where at least one of the fluids is a dense gas.
  • European Specification No. 0,547,575 relates to a membrane gas separation module containing a bundle of hollow fibres and a conforming sleeve around the fibres to reduce the bypass factor.
  • British Specification No. 2,268,096 describes a process and a device for continuous extraction of chemical substances by passing solute fluid on one side of a semipermeable membrane and passing extracting fluid on the other side.
  • the extracting fluid may be a gas or a pressurized dense gas.
  • the membrane is semipermeable and may be dense or porous. However, no specific porous membrane therefor is exemplified_
  • Pawliszyn Gas Extraction Kinetics of Volatile Organic Species from Water with a Hollow Fibre Membrane; Analytical Chemistry, 64(18), pp. 2101-2106, September 1992, discusses the extraction of VOCs from water through a membrane using a gaseous stripping medium. Nonporous membranes were found to be beneficial relative to porous membranes. Yang, M.J. and J. Pawliszyn: Extraction of Semivolatile Organic Compounds from Aqueous Samples Using High-Density Carbon Dioxide and Hollow Fibre Membrane Module; Analytical Chemistry, 65(18), pp. 2538-2541, September, 1993, relates to an extraction in which a nonporous silicone rubber membrane was selected to prevent dissolution of water in the carbon dioxide.
  • Shell-side fiber bypassing is a phenomenon in which a significant portion of the fibers within the module are bypassed by the shell-side fluid. Consequently, only a fraction of the total fiber surface area is utilized, making the module relatively inefficient. This phenomenon can render as much as 70%-90% of the membrane surface area ineffective. Id .
  • modules have attempted to reduce this bypassing problem by creating a baffle within the module that forces the shell-side fluid to contact more of the membrane surface area.
  • this technique does not solve shell-side fiber bypassing and also adds to the production cost of the module. Therefore, it is desirable to have a method and system for extracting a solute from a fluid using porous hollow fiber membranes, in which shell-side fiber bypassing is reduced and mass transfer efficiency is improved.
  • This invention is directed at a method of extracting a solute from a fluid comprising the steps of providing a membrane having opposite sides in a module under pressure with the membrane serving as a barrier interface between two fluids, providing one of the fluids into the module on one side of the membrane and the other fluid on the opposite side thereof, at least one of the fluids containing a solute to be extracted, and the other fluid serving as an extracting medium, the pressure on both sides of the membrane in the module being essentially the same, and extracting the solute across the membrane as driven by the concentration gradient of the solute between the fluids.
  • the membrane is porous and non-selective for the solute, and one of the fluids is a dense gas, the dense gas having a density of at least about 0.5 g/cc, and the fluid and dense gas being essentially immiscible in one another so as to provide two phases.
  • the method also may include the step of drying the membrane with the dense gas prior to the step of providing the fluid on the opposite side of the membrane.
  • the dense gas and fluid are passed countercurrently on the opposite sides of the membrane. While a static system reaches equilibrium quickly, passing the fluid and dense gas maintains a concentration gradient over time, and a countercurrent flow enhances the gradient.
  • the dense gas may be selected from a number of different gases, with carbon dioxide being preferred.
  • carbon dioxide is nontoxic, nonflammable, relatively inert, and leaves no residue in the extracted product.
  • dense gases include methane, ethane, propane, butane, isobutane, ethene, propene, tetrafluoromethane, chlorodifluoromethane, dinitrogen monoxide, sulphur hexaflouride, ammonia, methyl chloride and hydrofluorocarbons.
  • the hydrofluorocarbons include partially fluorinated methanes, ethanes and propanes, such as fluoromethane, trifluoromethane, tetrafluoroethane (known commonly as HFC-134a), 1, 1, 1, 2, 3, 3, 3-heptafluoropropane (known commonly as P227), HFC-143a and HFC-125, and mixtures thereof.
  • the fluid may be any of a number of different fluids, for example, fruit juice, fruit puree, vegetable juice, vegetable puree, oil-in-water emulsions, live cell fermentor broth and enzyme broth.
  • the fluid may be a second dense gas having a density of at least about 0.5 g/cc.
  • the solute to be extracted may be any solute with some solubility in both the fluid and dense gas, and typically is a flavor, fragrance, pharmaceutical or cheated metal.
  • the method typically is conducted within a temperature range of from about -10°C to about 200°C, and a pressure range of from about 2x10 5 Pa (2 bar) to about 7x10 7 Pa (700 bar).
  • This temperature range encompasses substantially all aqueous biological systems, and the pressure range encompasses operating pressures for both analytical and commercial-scale systems.
  • the invention is also directed at a system for extracting a solute from a fluid, comprising two fluid supply sources and a pressurizable module containing a membrane, the module being connected to the fluid supply sources for receiving each fluid on a respective side of the membrane, the membrane being adapted to serve as a barrier interface between said fluids, at least one of said fluids containing a solute to be extracted by a concentration gradient of said solute between said fluids, the other fluid serving as an extracting medium, and means for recovering said extracted solute.
  • the membrane is porous and non-selective for said solute
  • one of the supply sources is a dense gas supply source adapted to supply a dense gas having a density of at least about 0.5 g/cc.
  • the system may include means for substantially equalizing the pressure of the dense gas and fluid before the dense gas and fluid enter the module.
  • the pressure equalizing means may include means for substantially preventing extraction of solute within the pressure equalizing means prior to extraction within the pressurizable module.
  • the system may include means for monitoring the dense gas, fluid and amount of solute transfer, as well as means for returning the gas and fluid to the dense gas and fluid supply sources after extraction of the solute.
  • the membrane is a hollow fiber membrane or bundle of hollow fiber membranes.
  • Use of hollow fiber membranes allows for a high contacting surface area within a given module.
  • other types of membranes may be used, such as, for example, a flat membrane configured in a spiral-wound membrane module or a plate frame.
  • the membrane itself may be made of any of a number of different materials including, for example, polypropylene, polyethylene, polytetrafluoroethylene, polyvinylidene difluoride, nylon, polysulfonate, polycarbonate, polyester, cellulose acetate, cellulose nitrate, cellulose and acrylic.
  • the pores preferably are essentially symmetrical so that the membrane will be minimally affected by any pin-hole defects in the membrane surface.
  • the diameter of the pores preferably is on the order of about 0.001 micrometer to about 1 micrometer, and more preferably, about 0.1 micrometer to about 0.2 micrometer.
  • the 0.1 micron to 0.2 micron range typically provides the best balance of flow characteristics combined with symmetrical pore structure.
  • the thickness of the membrane preferably is on the order of about 0.005 mm to about 3 mm, and more preferably, about 0.2 mm to about 0.6 mm. These ranges provide an increasingly better balance of membrane strength and integrity combined with desired flow characteristics.
  • One of the advantages of the inventive method and system is improved mass transfer efficiency through reduced shell-side fiber bypassing.
  • dense gases In contrast to traditional liquids, dense gases have generally lower viscosities and higher diffusion coefficients. These properties allow a dense gas to distribute to and penetrate much more of the fiber surface within the module, thereby improving transfer efficiency.
  • a further advantage is the unexpected ability of the dense gas to dry the porous membrane prior to introduction of the fluid, thereby minimizing the potential for membrane wetting once the fluid is introduced and improving mass transfer efficiency.
  • Another advantage is the ability to pass a dense gas through the module at a faster rate than traditional liquid solvents. Flow rate is an important factor in transfer efficiency, but flow rate with traditional liquid is limited because of adverse frictional forces and increased shell-side fiber bypassing. Because dense gas generates less friction within the module, it may be passed at a higher rate, improving transfer efficiency.
  • a further advantage is the ability of the dense gas to occupy the pores of the membrane during extraction, thereby reducing the thickness of the boundary layer where extraction is occurring and improving mass transfer efficiency.
  • the dense gas does not induce wetting of the membrane pores by the fluid once the fluid enters the module. Therefore, the fluid on the side of the membranes opposite that of the dense gas may be passed through the module at a higher rate without displacing the dense gas from the pores, thereby improving mass transfer efficiency.
  • FIG. 1 A system for extracting a solute from a fluid according to the principles of this invention is shown in Fig. 1.
  • the system 10 includes a dense gas supply 12 and a fluid supply 14 for providing a dense gas and fluid to a pressurizable module 16, where extraction of a solute takes place.
  • the system 10 also includes a U-tube separator 18 operatively connected to the pressurizable module 16, for recovering the extracted solute from the extracting medium.
  • the dense gas supply 12 includes a gas tank 20 and a flow control unit 22.
  • the gas tank 20 is a standard gas tank such as a tank filled with CO 2 pressurized to 70,000 Pa (1000 psi).
  • the flow control unit 22 is an integrated system of a pump with pressure, temperature and flow controls, adapted to convert the gas to a dense gas having a density of at least about 0.5 g/cc and to provide a gross flow control for the dense gas going into the remainder of the system 10.
  • the fluid supply 14 is housed in a pressurizable reservoir 24 having a sealable opening (not shown).
  • the reservoir 24 may be opened to add additional fluid and/or solute.
  • the pressurizable reservoir 24 also serves as a means for substantially equalizing the pressures of the dense gas and fluid, and because the reservoir 24 is situated prior to the module 16, the dense gas and fluid will have substantially the same pressure as they pass through the module 16.
  • the pressurizable reservoir 24 further includes a floating diaphragm 26 disposed between the fluid and the dense gas. The diaphragm 26 has a diameter approximating the inner diameter of the reservoir 24, and substantially prevents extraction of any solute within the pressurizable reservoir 24.
  • a floating diaphragm 26 is used.
  • the pressurizable module 16 is shown in greater detail in Fig. 2.
  • Each hollow fiber membrane 28 terminates in a potting member 31 at opposite ends of the module 16.
  • the bundle 30 is surrounded by a shell 32, with each potting member 31 sealed to either end of the shell 32.
  • This shell 32 is further encased in a housing 34, using Buna N O-rings 56 to secure the shell 32 within the housing 34.
  • the housing 34 typically is made of stainless steel, and other metals or materials capable of operating at system pressures may be used if desired.
  • the membrane 28, potting members 31 and shell 32 typically are made of polypropylene but may be made of any of a number of other materials such as, for example, polyethylene, polytetrafluoroethylene, polyvinylidene difluoride, nylon, polysulfonate, polycarbonate, polyester, cellulose acetate, cellulose nitrate, cellulose or acrylic.
  • the membrane material may be selected based upon whether a hydrophobic or hydrophilic property is desired. For example, if an aqueous fluid is passed through the module 16, then a hydrophobic membrane 28 may be desired. The hydrophobic membrane 28 will repel the aqueous fluid from the membrane pores, enabling the fluid to be passed through the module 16 at a higher rate without displacing the dense gas from the pores. Alternatively, if an oil or other hydrophobic fluid is used, then a hydrophilic membrane 28 is desired for the same reason. In both cases, mass transfer efficiency is improved.
  • the module 16 has a fluid inlet port 36 and a fluid outlet port 38 operatively connected to the module 16 so that the fluid passes through the module 16 on the lumen side 44 of the porous hollow fiber membranes 28.
  • the module 16 also has a dense gas inlet port 40 and a dense gas outlet port 42 operatively connected to the shell side 46 of the membranes 28. In this way, extraction occurs across the porous hollow fiber membranes 28 along a concentration gradient, with the solute moving from the fluid on the lumen side 44 across the membranes 28 to the dense gas on the shell side 46.
  • the dense gas supply line 48 and fluid supply line 50, as well as dense gas and fluid outflow lines 52, 54, may be connected to the module 16 so that the fluid flows through the module 16 on the shell side 46 while the dense gas flows through on the lumen side 44.
  • the pressurizable module may be built in accordance with the construction technique and principles of Robinson U.S. Patent No. 5,015,585.
  • the U-tube separator 18 is connected to the dense gas outlet port 42 via a dense gas outflow line 52. As the dense gas charged with solute passes through the separator 18, the gas expands and the extracted solute is recovered in the separator 18.
  • the system may be configured so that the solute is extracted from the dense gas to the fluid.
  • a product recovery unit would be connected to the fluid outlet port 38 via the fluid outflow line 54 so that the solute could be recovered from the fluid using any of a number of known separation techniques such as distillation and the like.
  • the extraction system depicted in Fig. 1 includes other components as well.
  • a fluid pump 70 is placed on the fluid supply line 50 and is used to actively pass the fluid through the pressurizable module 16. Furthermore, the pump 70 may be set at different rates, thereby allowing the user to control the rate at which fresh fluid is passed through the module 16.
  • the system 10 includes several flow control devices for controlling the fluid and dense gas before and after passage through the module 16.
  • the dense gas inlet valve 72 controls the entry of dense gas into the dense gas supply line 48
  • the fluid inlet valve 74 located at the base of the pressurizable reservoir 24, controls the flow of fluid from the fluid supply 14.
  • the flow of dense gas through the system 10 also is controlled by a dense gas flow control valve 76, located along the dense gas outflow line 52 between the dense gas outlet port 42 and U-tube separator 18.
  • the system 10 includes several monitoring devices for monitoring the flow of fluid and dense gas.
  • a fluid sample valve 78 and dense gas sample valve 80 allow the user to selectively bypass the module 16, sending the fluid and/or dense gas through the remainder of the system 10 without extraction of solute.
  • the system 10 includes a fluid flow meter 82 and a dense gas flow meter 86.
  • the system 10 also includes a fluid totalizer 84 and dense gas totalizer 88 for measuring the total volumes of fluid and dense gas passing through the system 10.
  • the extraction of solute is measured using a light absorption detector 90.
  • the detector 90 is connected to dense gas and fluid outflow lines 52, 54 by a multiposition valve 96, allowing the user to selectively pass a dense gas or fluid sample through the detector 90.
  • a carrier fluid pump 94 pumps a carrier fluid through the carrier fluid line 92 and multiposition valve 96 into the detector 90.
  • the carrier fluid may be used as needed to dilute the dense gas or fluid being measured by the detector 90, and should be a carrier fluid that has no ultraviolet absorbance and is capable of dissolving both the fluid and dense gas solvents.
  • methanol is an appropriate carrier fluid when water and dense CO 2 are used.
  • Fluid not sampled to the light absorption detector 90 moves through the multiposition valve 96 to the fluid return line 98 and flows back into the pressurizable reservoir 24. Meanwhile, the dense gas not sampled is exhausted to the atmosphere at an ambient pressure after passing through a dense gas volume expansion unit 100 connected to the dense gas outflow line 52. If desired, the system 10 may be adapted to recycle the gas from the dense gas outflow line 52 back to the flow control unit 22 for repressurization and reuse via a gas return line (not shown).
  • the system 10 has a pressure maintenance line 102 connected to the dense gas supply line 48 and fluid outflow line 54.
  • This line 102 has a one way check valve 104 and provides an additional means for maintaining pressure in the system 10.
  • a one way check valve 106 in the fluid outflow line 54 also helps stabilize pressure.
  • a mass flow sensor 112 and heat exchanger 110 are included along the fluid supply line 50 leading to the module 16.
  • a fluid containing a solute to be extracted is placed in the pressurizable reservoir 24 and the reservoir is then sealed.
  • the hollow fiber membranes 28 are dried and the system 10 is pressurized by slowly opening the dense gas inlet valve 72, with the dense gas flow control valve 76 closed during this start up.
  • both the lumen side 44 and shell side 46 of the hollow fiber module 16 contain dense gas at the selected process pressure.
  • the dense gas also fills the head space of the pressurizable reservoir 24, thereby equilibrating the pressures of the dense gas and fluid within the system 10.
  • fluid is pumped into the module 16 by opening the fluid inlet valve 74 and selecting the desired stroke setting on the pump 70. Simultaneously, the dense gas flow control valve 76 is opened to provide the desired dense gas flow rate as shown on the dense gas flow meter 86.
  • the fluid is passed through the module 16 on one side of the porous hollow fiber membrane 28 and the dense gas is passed countercurrently through the module 16 on the other side of the membrane 28.
  • the fluid is passed on the lumen side 44 while the dense gas passes on the shell side 46.
  • these may be reversed by reversing the locations of the various supply and outflow lines.
  • solute extraction is driven by a concentration gradient. Because the pressurizable reservoir 24 has substantially equalized the pressures between the dense gas and fluid, the pressure differential across the membranes 28 is minimal.
  • the dense gas charged with solute passes through the dense gas outlet port 42 and into the dense gas outflow line 52.
  • the dense gas continues on through the multiposition valve 96 and dense gas flow control valve 76 to the U-tube separator 18, where the solute is recovered from the gas, and the gas is exhausted to the atmosphere.
  • the fluid stripped of solute passes through the fluid outlet port 38 into the fluid outflow line 54, and on through the fluid sample valve 78 and multiposition valve 96.
  • the fluid then flows back to the pressurizable reservoir 24 via the fluid return line 98.
  • the user also may measure solute extraction by passing a sample of dense gas or fluid through the light absorption detector 90.
  • the system may be reconfigured so that the solute is extracted from the dense gas to the fluid.
  • a product recovery unit such as a distillation chamber or the like, is placed along the fluid outflow line 54 so that the solute may be recovered from the fluid.
  • FIG. 3 Another preferred embodiment according to the principles of the invention is shown generally in Fig. 3.
  • This embodiment is a continuous system in which the dense gas is recycled back into the system after having passed through the module.
  • This alternative embodiment is similar in principle to the system of Fig. 1 with a few deviations. The primary difference is the addition of a gas return line 126, carrying the gas from the solute recovery unit 120 back to the gas flow control unit 22 where the gas is reconverted to a dense gas for continued use within the system.
  • the fluid supply 14 is separated from the pressure equalization element.
  • the fluid supply 14 has a sealable filling port (not shown) and is connected to a fluid flow control unit 118 which pressurizes the fluid.
  • the pressurized fluid and dense gas pass from their respective flow control units 118, 22 into the fluid supply line 50 and dense gas supply line 48, where their pressures are substantially equalized by a pressure equalization chamber 122 connected to the two supply lines.
  • the chamber 122 has a floating diaphragm 26 similar to the diaphragm of Fig. 1. Unlike the system 10 shown in Fig. 1, however, this embodiment does not have a fluid pump 70.
  • a fluid flow control valve 124 allows the user to control the rate at which the fluid passes from the fluid outflow line 54 into the extracted fluid line 98 and into the extracted fluid collector 128. If desired, this embodiment also may include various control and monitoring devices discussed above.
  • This example illustrates the extraction of caffeine from water using dense CO 2 as the extracting medium, according to the principles of the inventive method and system.
  • the extraction system used for this example is shown in Fig. 4 and is a simplified version of the system illustrated in Fig. 1 discussed above.
  • Extractions were performed using a standard gas tank 20 containing CO 2 at a pressure of 70,000 Pa (1000 psi), and a 300 cc pressurizable reservoir 24.
  • the pump 70 was an LDC brand positive displacement, variable stroke pump with a saphire plunger, having a flow rate of 7.5 cc/min at the 100% stroke setting.
  • the material used for the reservoir 24 was No. 316 stainless steel, and the tubing connecting the various elements was 3.2 mm (1/8") stainless steel.
  • the pressurizable module 16 used in this example was constructed of polypropylene and stainless steel. Polypropylene was used for the porous hollow fiber membranes 28, the shell 32 and the potting members 31.
  • the housing surrounding the shell was made from No. 316 stainless steel 25 mm (1") tubing having a wall thickness of 2.8 mm (0.109"), and the shell was secured within that housing using Buna N O-rings 56.
  • the polypropylene shell 32 had a length of 41 cm (16") and an outside diameter of 18-20 mm (0.7/8").
  • the module contained three porous hollow fiber membranes 28, with each membrane having a length of 41 cm (16"). Furthermore, each membrane had an inside diameter of 0.6 mm, an outside diameter of 1.0 mm, a pore size of 0.2 ⁇ , and a porosity of 75%.
  • the overall surface area provided by the three membranes 28 was 40 cm 2 .
  • the hold-up volume of the module was 0.33 ml for the liquid and 5.1 ml for the dense CO 2 .
  • the flow meter 86 was a rotameter, and the totalizer 88 was a conventional flow totalizer/dry test meter.
  • the system used in this example also included a few additional elements.
  • the dense gas supply line 48 had a moisturizer 134 for saturating the incoming dense gas with water.
  • the moisturizer 134 was a 100 cc cylinder filled with 3 mm glass beads and 15 cc water.
  • the dense gas outflow line 52 included a heated expansion valve 130 which warmed the dense gas before the gas stopped.
  • the total amount of CO 2 used was indicated on the totalizer 88 as liters at one atmosphere and ambient temperature. This volume was converted to grams of CO 2 for presentation in Table 1.
  • the temperature was ambient, and therefore the CO 2 was subcritical. However, at the pressures used, 98, 210 and 280 kPa, (1400, 3000 and 4000 psi,) the CO 2 had a density of about 0.8, 0.9 and 0.95 g/cc, respectively. In experimental runs 8, 9 and 10, the dense CO 2 was saturated with 0.1-0.2% H 2 O as it passed through the moisturizer 134.
  • the material recovered in the U-tube separator 18 was a concentrated solution of caffeine in water.
  • the separator 18 was rinsed out with acetone and combined with the acetone wash of residue in the heated expansion valve 130. After evaporation in a dish, the crystalline caffeine was weighed to the 0.1 mg, and the amount of caffeine recovered from each experimental run is shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Medicines Containing Plant Substances (AREA)

Claims (25)

  1. Procédé pour extraire un soluté d'un fluide comprenant les étapes consistant à :
    placer une membrane (28) ayant des faces opposées dans un module (16) sous pression, cette membrane servant de barrière entre deux fluides,
    introduire un des fluides dans le module (16) sur une face (44, 46) de la membrane (28) et l'autre fluide sur sa face opposée (46, 44), au moins un des fluides contenant un soluté à extraire et l'autre servant de milieu d'extraction, les pressions dans le module (16) de chaque côté de la membrane (28) étant sensiblement les mêmes et
    extraire le soluté à travers la membrane sous l'effet du gradient de concentration du soluté existant entre les fluides,
       caractérisé en ce que la membrane (28) est poreuse et non sélective vis à vis du soluté et en ce que l'un des fluides est un gaz dense, sa densité est au moins d'environ 0,5g/cc, le fluide et le gaz dense étant essentiellement non miscibles de manière à constituer deux phases.
  2. Procédé selon la revendication 1, comprenant l'étape consistant à sécher la membrane (28) avec le gaz dense avant de faire s'écouler le fluide sur la face opposée (44, 46) de la membrane.
  3. Procédé selon la revendication 1 ou la revendication 2, dans lequel on fait passer en même temps le gaz dense et le fluide sur les faces opposées (44, 46) de la membrane (28).
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel le fluide est choisi dans le groupe composé des jus de fruits, purées de fruits, jus de légumes, purées de légumes, émulsions huile dans eau, bouillons de fermentation de cellules vivantes et bouillons enzymatiques.
  5. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel le fluide est un second gaz dense dont la densité est au moins d'environ 0,5g/cc.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel le soluté est un arôme, une fragrance, un produit pharmaceutique ou un métal chélaté.
  7. Procédé selon l'une quelconque des revendications précédentes, ce procédé étant mis en oeuvre à température de l'ordre de -10°C à 200°C.
  8. Procédé selon l'une quelconque des revendications précédentes, ce procédé étant mis en oeuvre à pression de l'ordre de 2 x 105Pa (2 bar) à 7 x 107 Pa (700 bar).
  9. Procédé selon la revendication 1, dans lequel le soluté est un arôme ou une fragrance, la membrane (28) est non sélective vis à vis de cet arôme ou cette fragrance et le gaz dense est le CO2, ce procédé comprenant les étapes consistant à faire passer le fluide et le CO2 dense en sens inverse sur les faces opposées (44, 46) de la membrane, au moins l'un, du fluide ou du CO2 dense, contenant l'arôme ou la fragrance à extraire alors que l'autre sert de milieu d'extraction.
  10. Dispositif (10) pour extraire un soluté d'un fluide, comprenant :
    deux sources d'alimentation en fluide (12, 14) et un module (16) susceptible d'être mis sous pression contenant une membrane (28), ce module étant connecté aux sources d'alimentation (12, 14) pour recevoir chacun des fluides sur une face respective (44, 46) de la membrane, celle-ci (28) étant adaptée pour servir de barrière entre ces fluides, au moins un des ces fluides contenant un soluté à extraire sous l'effet du gradient de concentration de ce soluté existant entre ces fluides, alors que l'autre sert de milieu d'extraction et
    des moyens (18) pour récupérer le soluté extrait,
       caractérisé en ce que la membrane (28) est poreuse et non sélective vis à vis du soluté et en ce qu'une des sources d'alimentation (12, 14) est une source en gaz dense (12) adaptée pour fournir un gaz ayant une densité au moins d'environ 0,5g/cc.
  11. Dispositif (10) selon la revendication 10, comprenant des moyens (36, 38, 40, 42) pour faire passer le gaz dense et le fluide sur les faces opposées (44, 46) de la membrane (28).
  12. Dispositif (10) selon la revendication 11, dans lequel les moyens d'acheminement (36, 38, 40, 42) sont adaptés pour faire passer en même temps le gaz dense et le fluide sur les faces opposées (44, 46) de la membrane (28).
  13. Dispositif (10) selon l'une quelconque des revendications 10 à 12 comprenant un moyen (24) pour équilibrer sensiblement les pressions du gaz dense et du fluide avant qu'ils ne pénètrent dans le module (16).
  14. Dispositif (10) selon la revendication 13, dans lequel les moyens (24) comprennent un moyen (26) pour empêcher l'extraction du soluté dans les moyens (24) pour équilibrer les pressions avant son extraction dans le module (16).
  15. Dispositif (10) selon la revendication 14, dans lequel le moyen empêchant l'extraction est un diaphragme flottant (26).
  16. Dispositif (10) selon l'une quelconque des revendications 10 à 15 comprenant les moyens (22, 24, 70, 72, 74, 76) pour commander l'écoulement du gaz dense et du fluide.
  17. Dispositif (10) selon l'une quelconque des revendications 10 à 16, comprenant des moyens (82, 86, 90) pour surveiller le gaz dense et le fluide ainsi que la quantité de soluté transféré.
  18. Dispositif (10) selon l'une quelconque des revendications 10 à 17, comprenant un moyen (98) pour faire revenir le gaz dense et le fluide à leur source d'alimentation respective (12, 14) après extraction du soluté.
  19. Dispositif (10) selon l'une quelconque des revendications 10 à 18 ou procédé selon l'une quelconque des revendications 1 à 8, dans lequel le gaz dense est choisi dans le groupe composé du méthane, éthane, propane, butane, isobutane, éthène, propène, hydrocarbure fluoré, tétrafluorométhane, chlorodifluorométhane, dioxyde de carbone, monoxyde de diazote, hexafluorure de soufre, ammoniac et chlorure de méthyle.
  20. Dispositif (10) ou procédé selon la revendication 19, dans lequel l'hydrocarbure fluoré est choisi dans le groupe composé des méthanes, éthanes et propanes partiellement fluorés.
  21. Dispositif (10) selon l'une quelconque des revendications 10 à 20 ou procédé selon l'une quelconque des revendications 1 à 9, 19 ou 20, dans lequel la membrane poreuse (28) est une membrane en fibre creuse.
  22. Dispositif (10) selon l'une quelconque des revendications 10 à 21 ou procédé selon l'une quelconque des revendications 1 à 9 ou 19 à 21, dans lequel la membrane (28) est faite en matériau choisi dans le groupe composé des polypropylène, polyéthylène, polytétrafluoroéthylène, difluorure de polyvinylidène, nylon, polysulfonate, polycarbonate, polyester, acétate de cellulose, nitrate de cellulose, cellulose et produits acryliques.
  23. Dispositif (10) selon l'une quelconque des revendications 10 à 22 ou procédé selon l'une quelconque des revendications 1 à 9 ou 19 à 22, dans lequel le diamètre des pores de la membrane (28) est de l'ordre de 0,001µm à 1µm et l'épaisseur de cette membrane est de l'ordre de 0,005mm à 3mm.
  24. Dispositif (10) ou procédé selon la revendication 23, dans lequel le diamètre des pores de la membrane (28) est de l'ordre de 0,1µm à 2µm et l'épaisseur de cette membrane est de l'ordre de 0,2mm à 0,6mm.
  25. Dispositif (10) selon l'une quelconque des revendications 10 à 24 ou procédé selon l'une quelconque des revendications 1 à 9 ou 19 à 24, dans lequel les pores de la membrane (28) sont sensiblement symétriques.
EP95908530A 1994-09-09 1995-01-17 Procede et systeme d'extraction d'un solute d'un fluide a l'aide d'un gaz dense et d'une membrane poreuse Expired - Lifetime EP0781162B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US08/303,445 US5490884A (en) 1994-09-09 1994-09-09 Method and system for extracting a solute from a fluid using dense gas and a porous membrane
US303445 1994-09-09
PCT/US1995/000600 WO1996007469A1 (fr) 1994-09-09 1995-01-17 Procede et systeme d'extraction d'un solute d'un fluide a l'aide d'un gaz dense et d'une membrane poreuse

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Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6214300B1 (en) 1994-12-02 2001-04-10 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Microencapsulation and electrostatic processing device
JPH0961315A (ja) * 1995-08-24 1997-03-07 Sharp Corp 雰囲気中不純物の捕集方法および分析装置
US5932101A (en) * 1996-08-29 1999-08-03 Eastman Chemical Company Process for fluid/dense gas extraction under enhanced solubility conditions
US5976220A (en) 1996-12-09 1999-11-02 3M Innovative Properties Company Diffusional gas transfer system and method using same
US6180422B1 (en) 1998-05-06 2001-01-30 International Business Machines Corporation Endpoint detection by chemical reaction
US6126848A (en) 1998-05-06 2000-10-03 International Business Machines Corporation Indirect endpoint detection by chemical reaction and chemiluminescence
US6824789B2 (en) 1998-05-20 2004-11-30 Kemin Industries, Inc. Method of extracting antioxidants from lamiaceae species and the extract products thereof
US6086768A (en) * 1998-09-08 2000-07-11 Porocrit L.L.C. Method for demulsification of emulsions containing dense gas and liquid and a surfactant
US6331272B1 (en) * 1999-01-12 2001-12-18 Porocrit, L.L.C. Method and membrane system for sterilizing and preserving liquids using carbon dioxide
US6926829B2 (en) * 2000-03-06 2005-08-09 Kvaerner Process Systems A.S. Apparatus and method for separating fluids through a membrane
GB0016312D0 (en) * 2000-07-04 2000-08-23 Zylepsis Ltd Separation method
US20060201342A1 (en) * 2005-03-01 2006-09-14 Paganessi Joseph E Use of porous metal membrane for treating liquid foods
WO2007074126A1 (fr) * 2005-12-27 2007-07-05 Shell Internationale Research Maatschappij B.V. Appareil de separation de gaz
WO2012020174A1 (fr) 2010-08-09 2012-02-16 Sarl Netdesist Procede et dispositif de traitement de materiel contamine
EP2960211A1 (fr) * 2014-06-25 2015-12-30 Université d'Aix-Marseille Dispositif pour extraire des polluants par membrane tubulaire de type multicanaux
EP3475402B1 (fr) 2016-06-24 2023-08-02 Cool Clean Technologies, LLC Procédé d'extraction de cannabinoïdes par le dioxyde de carbone liquide
CN110632200B (zh) * 2019-09-27 2022-03-01 四川师范大学 一种基于温室气体的气泡萃取装置及其实现样品挥发性成分的高效分析方法
CA3190248A1 (fr) * 2020-07-10 2022-01-13 Clean Imagineering LLC Procede semi-aqueux d'extraction d'une substance

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2947687A (en) * 1954-10-29 1960-08-02 American Oil Co Separation of hydrocarbons by permeation membrane
US3477856A (en) * 1965-11-10 1969-11-11 Us Agriculture Process for extraction of flavors
US4113886A (en) * 1977-09-28 1978-09-12 General Foods Corporation Membrane decaffeination
IT7920188A0 (it) * 1979-02-14 1979-02-14 Montedison Spa Impiego di fibre sintetiche nella separazione dei succhi di frutta dai prodotti solidi della loro lavorazione.
US4341804A (en) * 1979-03-26 1982-07-27 General Foods Corporation Decaffeination of aqueous roasted coffee extract
DE3416519A1 (de) * 1983-05-20 1984-11-22 Linde Ag, 6200 Wiesbaden Verfahren und vorrichtung zur zerlegung eines gasgemisches
JPS6099328A (ja) * 1983-11-04 1985-06-03 Toyota Central Res & Dev Lab Inc 凝縮性ガス分離装置
DE3443390A1 (de) * 1984-11-28 1986-05-28 Hopfenextraktion HVG Barth, Raiser & Co, 8069 Wolnzach Verfahren zur abtrennung von coffein aus verfluessigten oder ueberkritischen gasen
FR2609413B1 (fr) * 1987-01-13 1991-01-11 Inst Francais Du Petrole Procede d'echange simultane de chaleur et de matiere a travers une paroi poreuse
US4820537A (en) * 1987-03-13 1989-04-11 General Foods Corporation Method for decaffeinating coffee with a supercritical fluid
US5015585A (en) * 1988-02-23 1991-05-14 Robinson James R Method and apparatus for culturing and diffusively oxygenating cells on isotropic membranes
CH679459A5 (fr) * 1988-05-04 1992-02-28 Bucher Guyer Ag Masch
JPH0330663A (ja) * 1989-06-28 1991-02-08 Toray Ind Inc アルコール飲料の製造方法
US4929357A (en) * 1989-08-09 1990-05-29 Exxon Research And Engineering Company Isocyanurate crosslinked polyurethane membranes and their use for the separation of aromatics from non-aromatics
US5338575A (en) * 1990-01-10 1994-08-16 Kohiensaure-werke Rud. Buse GmbH & Co. Process for the quasi-continuous decaffeination of raw coffee
US5149340A (en) * 1991-03-12 1992-09-22 Marathon Oil Company Process and apparatus for separating impurities from hydrocarbons
US5169529A (en) * 1991-04-22 1992-12-08 Hoechst Celanese Corporation Liquid membrane modules with minimal effective membrane thickness and methods of making the same
US5204003A (en) * 1991-05-08 1993-04-20 The United States Of America As Represented By The United States Department Of Energy Separation processes using expulsion from dilute supercritical solutions
US5236474A (en) * 1991-09-13 1993-08-17 Bend Research, Inc. Membrane-based removal of condensable vapors
TW207964B (fr) * 1991-12-16 1993-06-21 Permea Inc
GB9208313D0 (en) * 1992-04-15 1992-06-03 Pawliszyn Janusz B Continuous separation of organic compounds from water with hollow fibre membranes and supercritical fluids
US5263409A (en) * 1992-04-24 1993-11-23 Bend Research, Inc. Membrane extraction of citrus bittering agents
US5281254A (en) * 1992-05-22 1994-01-25 United Technologies Corporation Continuous carbon dioxide and water removal system
NL9201226A (nl) * 1992-07-08 1994-02-01 Tno Werkwijze en inrichting voor het reguleren van de vochtigheid van een gasstroom en het tegelijkertijd zuiveren daarvan van ongewenste zure of basische gassen.
US5395636A (en) * 1993-07-26 1995-03-07 Pall Corporation Method of pretreating a porous medium

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
F.PRATT AND J.PAWLISYN: "Water Monitoring System Based on Gas Extraction with a Single Hollow Fiber Membrane and Gas Membrane Chromatographic Cryotrapping", ANALYTICAL CHEMISTRY, vol. 64, no. 18, pages 2107 - 2110 *
F.PRATT AND J.PAWLIZYN: "Gas Extraction Kinetics of Volatile Organic Species from Water with a Hollow Fiber Membrane", ANALYTICAL CHEMISTRY, vol. 64, no. 18, pages 2101 - 2106 *
KIRK-OTHMER: "Supercritical fluids", ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, no. SUPP, NEW-YORK, pages 873 - 878 *
M.J.YANG AND J.PAWLISZYN: "Extraction of Semivolatile Organic Compounds from Aqueous Samples Using High Density Carbon Dioxide and Hollow Fiber Membrane Module", ANALYTICAL CHEMISTRY, vol. 65, no. 18, pages 2538 - 2541 *
R.PRASAD & K.K.SIRKAR: "Dispersion-Free Solvent Extraction with Microporous Hollow-Fiber Modules", ALCHE JOURNAL, vol. 34, no. 2, pages 177 - 188 *

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SK26597A3 (en) 1997-09-10
AU1681595A (en) 1996-03-27
CA2198872A1 (fr) 1996-03-14
BR9508827A (pt) 1997-08-12
DK0781162T3 (da) 1999-08-16
DE69506566T2 (de) 1999-05-06
KR970705429A (ko) 1997-10-09
NO971031L (no) 1997-03-06
ATE174232T1 (de) 1998-12-15
AU685235B2 (en) 1998-01-15
CA2198872C (fr) 2001-08-28
PL176944B1 (pl) 1999-08-31
CZ67397A3 (en) 1997-09-17
PL319077A1 (en) 1997-07-21
WO1996007469A1 (fr) 1996-03-14
MXPA97001737A (es) 2004-08-20
NO971031D0 (no) 1997-03-06
FI970941A (fi) 1997-05-07
FI970941A0 (fi) 1997-03-05
EP0781162A1 (fr) 1997-07-02
NZ279633A (en) 1997-12-19
ES2129807T3 (es) 1999-06-16
DE69506566D1 (de) 1999-01-21
JP3367677B2 (ja) 2003-01-14
US5490884A (en) 1996-02-13
JPH10507681A (ja) 1998-07-28

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